Crystal structure of [Ph3PCH2CH2PPh2+3][Ru10(μ6-C)2(CO)20(μ-CO)2-4] · 2Me2CO and some brief comments on the severely disordered structure of [NEt+4]2[Ru10(μ6-C)2(CO)20(μ-CO)2-4]

Oxidative Substitution of [Ru10C2(CO)24]2- with Disubstituted Alkynes: Facile Formation and Reduction of Ru10C2(CO)23(C2RR‘)

“…The decaruthenium cluster anion [Ru 10 C 2 (CO) 24 ] 2- ( 1 ) has a structure that can be viewed as two Ru 6 C octahedra sharing a common edge …”

Reversible Transformation between Methylene and Methylidyne-Hydride Moieties on the Ru10C2Framework

“…In compound 1 , the apical Ru4−Ru5 distance (3.071(1) Å) bridged by the methylene ligand is only slightly shorter than the apical Ru−Ru distances (3.122(2) and 3.138(2) Å) considered nonbonding in [Ru 10 C 2 (CO) 24 ] 2- , and the opposite apical Ru1−Ru8 distance (3.106(1) Å) falls in between. This situation contrasts with that displayed in the structure of Ru 10 C 2 (CO) 23 (C 2 Ph 2 ),7b in which there is one very short apical−apical distance (2.738(2) Å) involving the bridging alkyne ligand and one very long apical−apical distance (3.892(2) Å).…”

“…Structural diagrams of 1 are shown in Figure . The overall geometry of the 10 ruthenium atoms is derived from the edge-shared bioctahedral framework displayed by the parent compound, and the methylene ligand symmetrically bridges apical ruthenium atoms Ru4 and Ru5. The NBD ligand chelates in the η 2 , η 2 mode to equatorial ruthenium Ru3 with distances to C3 and C4 (2.17(1) and 2.17(1) Å) that are marginally shorter than those to C6 and C7 (2.19(1) and 2.20(1) Å).…”

“…Reversible transformations among the simplest C 1 fragments, CH, CH 2 , and CH 3 , are of particular interest as probes of hydrogen atom transfer between carbon and metal centers. , Higher nuclearity clusters incorporating these simple ligands are relatively rare, although the structural and electronic flexibility of such cluster frameworks may more closely approach the surface properties of catalytically active metal particles . In previous work we have shown that the higher nuclearity cluster system based on [Ru 10 C 2 (CO) 24 ] - is especially robust, undergoing direct thermal substitution with such four-electron hydrocarbon ligands as diphenylacetylene, allene, and norbornadiene to form [Ru 10 C 2 (CO) 22 (C 2 Ph 2 )] 2- ,7a [Ru 10 C 2 (CO) 22 (C 3 H 4 )] 2- , 8a,b and [Ru 10 C 2 (CO) 22 (NBD)] 2- , 8a,c respectively. These anionic clusters also undergo oxidative substitution with a ferrocenium/ligand combination to form further derivatives. 7b,8a We now report the synthesis of the methylene derivative Ru 10 C 2 (CO) 22 (NBD)(CH 2 ) and demonstrate its reversible interconversion with a methylidyne-hydride tautomer (see Scheme ).…”

Medium- and High-nuclearity Clusters of Ruthenium and Osmium

“…279 The monocarbido cluster [Ru 10 (|i 6 -C)(CO) 24 ] 2 " (214) is isolated in 81% yield from redox condensation between (110) and Ru 3 (CO) 12 . 266 Its isostructural osmium analogue [bs, 0 (n 6 -C)(CO) 24 ] 2~ (215) is obtained from the vacuum pyrolysis of Os 3 (CO) n (py) or Os 3 (CO), 2 , ' 268 and from the pyrolysis of [Os 6 (CO) 18 ] 2~ (101) in triglyme.…”